July 10, 1923. 1,461,646 H. F. FRENCH ET AL MATERIAL FOR PRODUCING SMOKE SCREENS Filed Jan. 14, 1919 at 2 INVENTOR HLEPRENCH ay CRO BENNER ATTORNEYPatented July 10, 1923. UNITED STATES 1,461,646 PATENT OFFICE. HARRY ¥. FRENCH AND RAYMOND C. BENNER, OF FREMONT, OHIO, ASSIGNORS TO NATIONAL CARBON COMPANY, INC., A CORPORATION OF NEW YORE. MATERIAL FOR PRODUCING SMOKE SCREENS, Application fled January 14, 1919, ferial No. 271,198, To all whom it may concern: Be it known that we, Haney F. Frencx and Raysoxp C. Benver, citizens of the United States, and residents, respeetively, 5 of Fremont, in the county of Sandusky an State of Ohio, and Fremont, in the county of Sandusky and State of Ohio, have invented a certain new and useful Improvement. in Materials for Producing Smoke Screens, of 10 which the following is a full, clear, and ex- act description. This invention relates to smoke produe- ing materials especially designed for use in smoke boxes for combating submarine wai 15 fare, The effectiveness of smoke boxes i combating submarine warfare depends upon quickly producing a large volume of opaque smoke around a vessel, or between the sub- marine and the vessel, in order to render 20 it invisible to the enemy. ‘The vessel is thus rendered a poor target for torpedoes dis. charged at it, and is enabled to elude the submarine, ‘This application is a continuation in part 28 of our prior application Serial No. 254,739 filed Sept. 19, 1918, which particularly ‘de- scribes ‘and claims the construction ‘of a smoke box adapted to utilize the smoke pro- ducing mixture, while the subject matter 30 and claims of this invention relate more par- ticularly to the composition of the snioke roducing mixture. It will be understood, Romever iat the smoke prodwcinn ares is not limited to use in smoke boxes for 38 submarine warfare. ‘The particular object of the present in- vention is to secure a smoke producing com- position which, although of light weight and consisting of relatively inexpensive ma- 40 terials, will quickly produce enormous vol. ‘umes of opaque smoke. ‘Other objects and. advantageous features of the invention will appear in the accom- panying description in connection with & 45 diagrammatic drawing illustrating in a simple manner the method of using a smoke producing, mixture. The single figure of the drawing shows a diagrammatic cross section through an ap- 20 paratus embodying the essential features of the smoke box of the original application, ‘The preferable manner of using the mix- ture is to enclose it in a receptacle or box 1 having openings 2 near the top. ‘The ma- 98 terial to be placed in the box may be di- vided into three portions, namely, the ig- nition. mixture, the starting mixture and the principal smoke producing mixture. ‘The starting mixture consists of a iayer 8 placed on the bottom of the box amount. ing to 8.8 Ibs. of a mixture containing pref erably one part of powdered charcoal to four parts of sodium nitrate by weight, though this may be varied. Each of these materials is erushed to pass through a six- mesh screen, At a certain point above this layer of starting mixture is placed the ig. nition mixture 4 which is arranged in the center of the box adjacent the starting mix- ture and enclosed in ‘a suitable easing 8 open at the bottom. The quantity of mixture used is preferably about 2 grams consisting of powdered charcoal and powdered potas: sium chlorate preferably in the proportion af one part of chareoal to ten parts of pota sium chlorate by weight, though this may he varied. Any’ suitable meang is provided for igniting the ignition material. As shown diagrammatically in the drawing, this consists of a resistance wire 6 passing through the ignition material and connected, by means of suitable conductors 7, 8 to an electric battery 8. ‘The crease is dosed aa any suitable manner as by means of the switch 10, in order to heat the ignition ma- terial toa temperature sufficient to start a reaction between the carbon and potassium chlorate. The principal smoke producing mixture consists of about 75 Ibs of 'w mistine ek hard pitch 1 part, antimony trisulphide 4 parts, sulphur 23” parts, sodium nitrate 8 parts, and ammonium chloride 4} parts, by ‘weight. The proportions of the smoke pro- ducing mixture may be varied within the following limits for the purposes hereafter set forth: pitch 1 part, antimony trisulphide 1 to 8 parts, sulphur } to 5 parts, sodium nitrate 3 to 15 parts and ammonium chlo- ride 1 to 10 parts. ‘The pitch and sodium nitrate are ground to pass through a six- mesh screen and the remaining materials are powdered. As shown in the drawing, the smoke producing mixture and starting mixture only about half fill the box and are held in place by a paper or eloth cover 11 and a piece of wire netting 12. -As soon as the circuit is closed through the resistance wire, the readily inflammable ignition material in the easing is heated to 0 % 80 100 10sthe point of ignition. A highly combustible material is supplied by the charcoal and potassium chlorate, as the latter decomposes very easily and supplies oxygen for the combustion of the charcoal. ‘The combustion of the charcoal produces sufficient heat to propagate the reaction to the starting mixture Which is adjacent to the ignition mixture. This mixture of char- coal and sodium nitrate also burns readily although in small quantities it does not pro- duce such vigorous reaction as the char- coal and potassium chlorate of the ignition material. ‘The amount of the starting mi jure is considerable anid the reaction is suf- ficiently vigorous to start full smoke evolu- tion almost instantaneously, but is not. so violent as to produce an explosion which would destroy the box. "An especially important’ feature of the present invention, is the ignition of the Smoke mixture from the bottom, This method of starting has proved to be very effective in producing quickly large vol- umes of sinoke, and also gives more uniform and certain reaction for a given period of time. ‘The reaction starts 50 quickly that about 10 to 20 seconds after cireuit is closed, large volumes of brownish-white smoke issue from the holes in the box, and this continues quite uniformly for 15 to 20 minutes, and by suitable changes these periods may be varied over a, wide’ range. Tis period, however, covers the time dur- jing which the smoke box is useful in sub- marine warfare. ‘The theory of operation of the smoké i ie about as follows, although we fare not limited to such, explanation —The heat from the burning of the pitch vapor- izes the ammonium ‘chloride which is the main. stoke ingredient, but if no other smoke ipaterial were used the vaporized ammonium chloride would react with the sodium oxide produced in some amounts by tthe reaction between the sodium nitrate and pitch, which would produce free ammonia, Sodium chloride and water. none of which ig a smoke producer. We have found that the formation of these materials is mini- mized by incorporating sulphur or a sul- phur material in the smoke mixture, and prefer to use free sulphur and antimony {risulphide. ‘These react with the other ma- terials to produce good “smoke” materials. ‘The principal ingredients in the smoke in the specific mixture used probably are am- monium chloride, sulphide, sulphite, sul- phate, and antimony chloride, oxide and pentasulphide. ‘The sulphur and antimony sulphide used also furnish heat: in entering into the combination referred to, and there- fore they Have a double purpose. |” ‘here are various equivalents for the in- 65 gredients disclosed. One could use other 10 w 6 50 85 60 1,461,648 powdered or granular carbonaceous ma- ferial then piteh, and arsenic, oxide, anti- mony trioxide, ete., could be substituted for amnionium chloride. Other oxygen carriers than sodium nitrate could also be employed, potassium nitrate for instance. Tn ease a darker colored smoke is desired, the pitch or other carbonaceous materi will be used in excess, so that incomplete combustion occurs. Infact, if black smoke js sought, pitch and sodium nitrate alone ‘admirably fulfill the requirement, provided the proportions are so manipulated as to get incomplete burning of the pitch. ‘By suitable changes the speed of the re- action may be varied as desired. By way of example, the speed of reaction between the smoke producing ingredients may be in. creased by. increasing, the proportion of heat forming materials and main smoke forming material. This is most readily ac- complished by diminishing the ammonium chloride content. The fuel consequently hhas less material to volatilize and therefore the production of smoke is more rapid, but naturally the duration of the production of 0 ™ _smoke per pound of material will be short- ened by the reduction of the main smoke producing material, and by the greater vol- ume of smoke produced per unit of time. ‘Having described our invention, what we aim ‘. A non-explosive smoke producing mix- ture containing » carbonaceous material, an oxidizing agent, and a smoke forming sub- stance vaporizable at a low. temperature. 9. A smoke producing mixture contai ing a sublimat smoke forming material _and. a combustible material for volatilizing said first mentioned material. 3. A smoke producing mixture contain- ing a sublimable chloride and a combustible material for volatilizing said first mentioned material. ‘4, A smoke producing mixture containing ‘a combustible material and an ammonium salt capable of forming opaque fumes when volatilized by combustion of the material. 5. A smoke producing mixture contain- ing ammonium chloride in combination with 2 combustible material and an oxidizing material adapted to react with the roduc- tion of heat enough to volatilize tl monium chloride. 6. A smoke producing mixture cont: ing’ ammonium chloride, « heavy, hydroca onaceous material and an alkali-metal trate, 7. A smoke producing mixture containing one to ten parts ammonium chloride in combination with one part of a heavy hy- Grocarbonaceous material and three to fif. teen parts of an oxidizing material adapted to react with the production of heat enough to volatilize the ammonium chloride. 105 0 ‘am- 10 125 101,461,040 8. A smoke producing mixture compris- ing a volatile smoke-forming. material, a combustible material and an oxidizing ma- terial adapted to combine to volatilize the 5 smoke-forming material leaving a residue Which would react with the smoke-forming material and a material adapted to com. bine with the residue to prevent said re. action. 10 9. A smoke Producing mixture containing sulphur and ammonium chloride in com bination with sodium nitrate and a com. bustible material adapted to react there. with with the production of heat enough to volatilize the ammonium chloride. 10. A smoke producing mixture contain- ing a sulphide and ammonium ebloride in combination with sodium nitrate and a heavy hydrocarbonaceous material. 20 11. A smoke producing mixture cont: ing a sulphide, elemental sulphur, an alkali. metal nitrate,’ a heavy hydrocarbonaceous material and ammonium chloride. «iz. A. smoke producing mixture contain- 25 ing antimony sulphide, elemental sulphur, ry 8 sodium nitrate, pitch and ammonium chlo- ride. 18. A. smoke producing mixture contain. ing antimony trisulphide 1 to 8 parts, sul. phur 3 to 5 parts, sodium nitrate 8 ¢0 18 Parts, pitch 1 part, and ammonium chloride 1 to 10 parts, 14. A smoke producing mixture contain. ing a sulphide and ‘a vaporizable smoke. forming material in combination with an idizing mi and a combustible ma- terial adapted to react therewith with the production of heat enough to volatilize the smoke-forming material 15. A smoke producing mixture contain- ing a sulphide and a vaporizable smoke forming material in combination with a ni. trate and a combustible material adapted to Teact therewith with the production of heat enough to volatilize the ammonium salt. In testimony whereof, we hereunto affix our signatures, RAYMOND (. BENNE! HARRY F. FRENCH. rR. 35 «o 4s